Preparation of hydrocarbon synthesis gas



July 6, 1954 G. A. VINCENT PREPARATION oF HYDRocARBoN SYNTHESIS GAS Original Filed Sept. 27, 1947 mmf Aww/mm Patented July 6, 1954 PREPARATION F` HYDROCARBGN SYNTHESIS GAS Gregory A. Vincent, Ridgewood, N. J., assignor to Y The M. W. Kellogg Company, Jersey City, N. J.,

a corporation of Delaware Continuation of application Serial No. 776,538,

September 27, 1947. This application November 28, 1951, Serial No. 258,623

duction of hydrogen Fand an oxide of carbon and the subsequent interaction of the hydrogen and the oxide of carbon inthe presence of a hydrogenation catalyst to produce hydrocarbons havn ing more than one carbon atom per molecule and oxygenated organic compounds.

This application is a continuation of my application Serial No.'776,538 iiled September 27, 1947, now abandoned.

It has been known for some time that a gaseous mixture comprising hydrogen and carbon monoxide may be produced either bythe partial combustion of relatively low-boiling hydrocarbons, such as methane, or by the reaction of relatively loW-boiling hydrocarbons with steam and/0r carbon dioxide. Y Thel partial combustion of methane as Well as the reaction of carbon dioxide With methane to produce hydrogen and carbon monoxide produces these components'in a relatively low ratio with respectto each other, usually in a mol ratio less .thanabout 2:1 .at temperatures between about 180.0 and `about 2500 F. Onthehother' hand, the production of hydrogen andcarbon monoxide by thereaction between methane and steam producesthese components in a mol ratio aboveiabout 2:1 `at a temperature of about 1250 to about-24000A 1i'.V

Either of the abovereactions may'beieffected with or Without a catalyst. i The synthesis of organic compounds fromsuch gaseous mixtures'has been eiected inthe presence of `a catalyst, such as a metal or a metal'oxide of vgroup VIII rof the periodic'table. Generally the mol ratiopf nhydrogen V to carbon monoxide for the synthesis of vorganic compounds is between about 1:1' andY about 3:1, preferably'a ratio of about 2:1. It is, therefore, desirable to provide a method for producing a synthesis feed having the preferred composition of about 2:1 mol ratio of hydrogen to carv 2 a normally gaseous hydrocarbon into normally liquid hydrocarbons.

Another object of this invention is to provide a more economic process for the synthesis of organic compounds from methane.

Other objects and advantages of the present invention will become apparent to those skilled in the art from the accompanying description and disclosure.

According to this invention, methane, or other normally gaseous hydrocarbon or mixture thereof, is converted simultaneously in separate zones to hydrogen and carbon monoxide by partial combustion With an oxygen-containing gas as the primary reaction in one zone'and by direct reaction with steam as the primary reaction in a second zone. The product of the methane conversion comprising hydrogen and carbon monoxide from each zone is combined as a synthesis feed mixture and passed through a synthesis reaction Zone undersuitable vconditions of operation and in the presence of a suitable catalyst, such` as iron, to producehydrocarbons having more than one carbon atom per molecule and oxygenated organic compounds as the principal products of the process. Unconverted reactants, carbon dioxide and methane from the synthesis reaction are recycled to one or both of the methane conversion zones, preferably to the methane reforming Zone when a considerable amount of carbon dioxide is produced inthe i; synthesis reaction zone. vBy effecting the synl thesis Vof organic compounds according to this jv invention the efliciency of. the process may be greatly increased and a synthesis feed gas of the n desired composition 'for' optimum yield of normally liquid organic'compounds may be proy duced.'

YInstead of the partial combustion of methane, conversion of coal or coke with steam and oxygen may be substituted therefor Without departing from the scope of this invention. The 'conversion ofcoal or coke may be effected with a moving bed of solids or with a uidized finely divided solids process known to those skilled in l the art. The eiiluent from the conversion of coal creases undesirable side reactions which results 3 in contaminating the synthesis catalyst with carbcn, tars, waxes and relatively high-boiling organic compounds. In this respect, the present process provides a method for producing a synthesis feed gas of the preferred composition.

For the best understanding of the present invention a description of the process according to the accompanying drawing will be undertaken.

The drawing comprises a diagrammatic illustration of an arrangement of apparatusfor the manufacture of hydrocarbons having more than one carbon atom per molecule` and oxygenated erganic compounds from methane. The apparatus of the drawing comprises a methane combustion unit 1, a methane reforming -unit I4, a synthesis reactor 2| and suitable auxiliary equipment.

According to the illustration of the present process in the drawing, methane or a methanecontaining gas from any suitable source, such as natural gas, after removal of HzS therefrom by conventional methods, is passed under pressure through conduit '6 to a combustion zone 1. Although methane is referred to specifically as the feed, the use of other gaseous hydrocarbons, such as ethane and propane, is within the scope of this invention. Oxygen or an oxygen-containing gas is passed to combustion unit 1 through conduit 8. Methane is preheated, such as by indirect heat exchange with the combustion products from the combustion zone of unit 1 as shown. Oxygen may also be preheated if desired. In combustion unit 1, methane is oxidized to hydrogen and carbon monoxide according to the typical equation shown below.

Combustion unit 1 may comprise Aa pressure vessel formed of va carbon steel shell capable of withstanding the pressure of operation and protected from excessive temperature by a cast lining of a suitable refractory material, such as zirconia, including a burner fabricated vof a heat resistant alloy and cooled by circulating Water or steam through it.

When the source of methane is natural gas, the feed gas composition will be approximately that shown in Table I below:

Table I Mol per cent N2 n CO2 0.5 CHi 79.7 02H6 12.1

CSI-I3 4.7

The temperature of combustionin unit '1 is between about 1700 and about 2600 F., preferably it is a temperature of about 1800 to about 1900 F'. when using a catalyst, such as nickel, and a temperature of about 2350 to about 2500 F. when not using a catalyst. A pressure between about one atmosphere and about 500 pounds per square inch gage corresponding substantially to the pressure in the subsequent synthesis reaction zone is maintained in combustion unit 1. Preferably, the reaction is effected with a catalyst comprising nickel or nickel oxide supported on a heat resistant support, such as alundum. The catalyst is maintained in a stationary bed in various forms, such as pellets or granules, porous tubes of ceramic material impregnated with catalyst, or tubes of the metal catalyst. The reaction is exothermic requiring only preheating of the methane stream to effect' reaction. The mol ratio of oxygen to methane entering the reaction zone is between about 0.521 to about 0.7:1. A reaction effluent comprising hydrogen and carbon monoxide in a mol ratio of less than about 2:1 is continuously removed from reaction unit 1 through conduit Il. Since the temperature of reaction is a function of the ratio of oxygen to methane, a specific ratio within the above range is chosen to give the desired temperature at which conversion is substantially complete and carbon formation is minimized. The specic mol ratio of hydrogen to carbon monoxide in the product 'from combustion unit 1 is between about 1.7:1 and about -1.9:1 when no tail gas is recycled from the synthesis reaction system. The composition of a typical reaction eiuent for the partial combustion of methane is shown below in Table II 'and it will be understood that such composition depends upon such operating conditions as ternperature, ratio of methane and oxygen, etc.

Although substantially pure oxygen is preferred as the oxidizing agent for the methane combustion, air or other loxygen-containing gas may be used also without 'departing from the scope of this invention. In order to recover exothermic heat of reaction liberated in the com- 'bustion zone 'of unit 1, indirectheat exchange of the reaction products with water to produce steam may be effected in conduit 9 as shown. The steam thus produced may be used for producing power, for heating purposes or may be lused in the reaction between methane and steam to be described more fully hereinafter.

Steam formed by the partial combustion of `methane in unit 1 may be `removed from the efliuent in conduit Il by cooling the eiiluent and condensing the steam therefrom, if desired.

Simultaneously, with the production of hydrogen and carbon monoxide'in combustion unit 1, methane is continuously passed from conduit S through conduit I2 to vreformingunit I4. VSteam is introduced into reforming unit I4 through conduit I3. Heat is supplied to reforming unit I4 by the combustion of a fuel in indirect heat exchange with the mixture of steam and methane to produce a temperature between about 1400 'and about 1600o F. Reforming unit I4 comprises a conventional tubular reforming furnace of the type known to those skill-ed in the art, with catalyst in the reaction tubes. The pressure of the reaction mixture of methane and steam the tubes of the reforming furnace M is usually below about 1'00 pounds per square inch gage and is preferably between about l5 and about 50 pounds per square inch gage. The ratio of steam to methane in the feed mixture to the reforming unit I4 is about 2 mols of steam per mol of methane, although higher 'ratios may be used without departing from the scope of this invention. Carbon -dioxide may be employed to replace a portion of the steam used, such as by recycling tail gas or carbon dioxide from the synthesis reaction. For example, one mol of steam and one mol of carbon dioxide may be employed per mol of methane. tions for the reaction of methane with steam and carbon dioxide are shown below:

'I'he interaction of methane with steam or carbon dioxide is eifected in the presence of a suitable catalyst in reforming unit I4. A suitable reforming catalyst may comprise nickel or nickel oxide supported on alumina or other supporting material, such as, for example, a catalyst containing in parts by weight 1 NiO, 0.2 CrzOs, 1.68 SiOz, 0.9 MgO. Other reforming catalysts comprise molybdenum, cobalt and chromium and their-oxides and suldes. The catalyst is maintained in a stationary bed of relatively small pieces of solid material in the tubes. A regeneraf tive type reformer furnace constructed of ceramic material may be used instead of the aforementioned tubular type furnace. With a regenerative type furnace heated at intervals by direct contact with combustion gases, temperatures as high as 2400 F. are possible, which high temperature obviates the necessity of a catalyst. A gaseous eilluent comprising hydrogen and carbon monoxide in a mol ratio greater than about 2 1, usually about 4:1 with no recycle and about 3:1 with recycle of tail gas or carbon dioxide, is removed from reforming unit I4 through conduit I6. aS-uch a gaseous efliuent has approximately a composition as shown in Table III below when natural gas is the source of methane. It will be understood that the composition of the elfluent will depend upon the reforming operating conditions, such as temperature, space velocity, steam to methane ratio, etc.

The eluent in conduit I6 is passed through. a cooler I'I for coolingrthe effluent to a temperature below aboutr 200 F. to condense the steam in the eiluent, which steam is removed as condensate from cooler I'I through conduit I5. Usually the effluent is cooled to a temperature of about 100 F. before compressing. From cooler II the reforming unit eiliuent is continuously passed through conduit I8 and compressed, if necessary, by a compressor (not shown) and then combined with ,.f'f

the eluent of combustion unit 'I leaving conduit I I. The resulting mixture Yfrom conversion units 'I and I4 is continuously passed through conduit I9 to a conventional synthesis reactor 2 I.

Synthesis reactor 2| may comprise any of several types of conventional reaction chambers, such as fixed bed or fluid bed reaction units, known to those skilled in the art, and may comprise several reactors in series or in parallel. The

combined synthesis feed in conduit I9 comprises hydrogen and carbon monoxide in a mol ratio of 2:1 or thereabouts. This feed is passed through synthesis reactor 2| in contact with a suitable catalyst, such as iron or other metal or metal oxide of group VIII-of the periodic table, under Typical equaconditions of reaction such that hydrocarbons havingmore than one carbon atom per molecule and oxygenated organic compounds are produced as products of the process. reaction in synthesis reactor 2| is usually between about 300 and about r100 F. and a pressure is maintained between about atmospheric and about 500 pounds per square inch gage, preferably between about 100 and about 300 pounds per square inch gage. When employing an iron or iron oxide catalyst, a temperature between about 450 and about 650 F. is appropriate. When employing a cobalt catalyst a temperaturebelow 450 F. is employed. Sufficient contact time of reactants and reaction products with the catalyst material is afforded in reactor 2| to form the desired products of the process. Usually, a contact time of gases with catalyst of about 2 to 20 seconds is appropriate.

A reaction efuent comprising hydrocarbons, oxygenated organic compounds, steam, carbon dioxide and unreacted reactants including some methane from the synthesis gas, is removed from Y reactor 2| through conduit 22 and passed to a primary condensation unit 23. Condensation unit 23 comprises a conventional condenser and accumulator and auxiliary equipment for partial condensation of the effluent. Unit 23 comprises a single or a series of /condensation units and accumulators. The temperature of the effluent in condensation unit 23 is reduced to about 300 F. or lower and the eluent in condensation unit 23 is maintained at substantially the same pressure as that existing in reactor 2 I. The cooling of the effluent results in the formation of either one or two liquid phases in `primary condensation unit 23. These liquid phases comprise a lighter hydrocarbon-rich phase and a heavier water-rich phase containing dissolved oxygenated organic compounds. Gases comprising hydrogen and/ or carbon monoxide and including methane and carbon dioxide are removed from condensation unit 23 through conduit 24 and may be recycled to.

synthesis reactor 2| through conduit 26 in order to supplement the composition with respect to any component of the synthesis feed in conduit I9 and to alter the ratio of hydrogen to carbon monoxide in reactor 2 I. When formed, the waterrich phase in primary condensation unit 23 is removed` therefrom through conduit 2IV and may be passed to subsequent conventional separation and recovery equipment (not shown) for the removal of dissolved oxygenated organic compounds therefrom as products of the process,

A portion or all of the uncondensed components of the eiuent from reactor 2| and the liquid hydrocarbon-rich phase are removed from condensation unit 23 through conduit 28 and passed to a secondary condensation unit 29 which may comprise a conventional lean oil circulating system known to those skilled in the art. Condensation unit 20 also comprises suitable condensers and acoumulators for further condensaton and accumulation of reaction products. The temperature of condensation unit 2S is maintained below about 100 F. and a pressure is maintained substantially equivalent to the pressure existing in synthesis reactor 2l.

Pressures higher than the pressures existing in reactor 2| and condenser 23 and/or refrigeration may be employed in connection with unit 2S without departing from the scope of this invention. kIn condensation unit 20 further condensation of the gaseous components is effected and an organic condensate is removed therefrom The temperature of v vtr through.l .conduitf i and passed eto subsequent f conventional separation andreoovery equipment (notfshovvn). for itherecoveryioffproducts .of-the process Any'water condensedin condensation unit 29 is withdrawntherefrorngthrough conduit 32.1: Uncondensed 'componentsfof the reaction eiiiuent.' comprising hydrogen. i and/0r. carbon monoxide, carbon dioxide', methaneand unrecovered hydrocarbonsr heavier than methane, are removed fromcondensation Iunit 2d through conduit'` and arerecycled inxwhole .or in part to. conduit Zandreorming unit It by means of recycle' conduits. 34; and "M1: A portion or all of the gases-or. vaporsirhmfthe primary condensation unit 23. may also` be. recycled to refor.l ing-unit kEll through conduitsv 24g-'34, il and IZ. Recycling oi Y,go-:ses `from condensation units 23 andZl to reformingunit lll is desirable in order to utilize the methane andfcarbon dioxide conte'ntfof y'the gases'ior. production' of 4additional synthesis gas.

Recycling ofat least aportion 'of the recycle gases to reforming unit i4 is. particularly desirablewhen the synthesis 'reactioncisy eiiected in the presence of an ironor .an iron oxide catalyst since with such a Vcatalyst the synthesis reaction effluent contains appreciable amounts of carbon dioxide;i With=a1reduced iron catalyst the composition of1 synthesisreaction eiu'ent maycomprise as -muchas 2O to 50 volume per cent carbon dioxide. As previously discussed, carbon dioxide' reacts withmethane, and, therefore, recycling of the carbon dioxide-rich gases to reforming unit lil is particularly desirable and results in a higher methane conversion at given conditions and in' aflo'wer endothermic reaction duty per unit of carbon-monoxide 'manufactured as comparedtviththe use-of steam and methane alone.

in someinStancesCWherethe carbon dioxide content fot-therecyclefgases is relatively low, such asbelowabout 20 -per-cenuand the `pressure existing on the l'recyclage-ses is approximately the Vsaine-'or higher -than-^in combustion unit fi, a portion of-therecycle gases-is conveniently and advantageously recycled to unit-'1 lto utilize the pressure ofthe'gases by avoiding compressonr'of the recycle gases and their `methane and hydrogen content.A

The pressure' of thedecycle gases 4is substantially the same as the pressureexisting in synthesis reactor 2iA whicliis usually `under a pressure substantiallythe same as that in combustion unit except for the additional pressure needed to induce flow through the system. If

the pressure in combustion unit i is lower than A that of the recycled gases, the pressure may be decreased by expansion into conduit E in which case compression will be eected in conduit Il or I8 by means not shown. However, if the pressure of the recycle gases is lower than the pressure existing in combustion unit 'I as Will usually be the case, a suitable compressor (not shown) must be provided in conduit 34 for raising the pressure of the recycle gases to the pressure existing in combustion unit l. Combustion unit l may be operated at substantially the same pressure as synthesis reactor 2l with no corn- 8". iicientxand economical under conditions-"ciccp: eration, or the recycling gases inconduit 34 may. bey divided and a portion passed izo-combustion. unit 'l and the other-.portionpassed to reformingl unit I4.

A typical composition of recycle gases is illustrated in TableIVfbeloW Wheniusing an iron synthesis catalyst 'and When recycling to reforming unit Ilf Table IV Mol percent N2 2.4' H2 47.4 CO 6.3 CO2 32B CH4' 8.5' C2i 3.1

Total 160.0

As is evident from the above typical composition a considerable amount of hydrogen and combined carbon is. present in the` recycle gases. The vpresence of .such components is a readily, available source of synthesis feed gas COJfHz) and, thus, therecyclelof 'the normally gaseous components of the synthesis effluent to the methane ccnversionunits is desirable. The hydrogen in the recycle gases is. notv only asource of hydrogen for the synthesis reaction, but is known to decrease carbon or coke formation during partial combustion of methane, such as is effected. in combustion unit 7.

It is to loe-understood that the ratio of. hydrogen to carbon monoxide. in the combined synthesis feed gas is a.-,1unction,.o ,both the total quantity of hydrogen andcarbon monoxide in each separate gasstreamand theratio. of hydrjo gen to carbon monoxide in each .separate 4gas stream, from combustion unit 'F 'and reforming unit lll. The total quantity oi hydrogen and carbon monoxide produced is a function of the quantity of raw materials freshly introduced and introduced by Way. oi the recycle gases, in order to. obtain a combined synthesis gas of a particular composition, the total quantity of hydrogen. and carbon monoxide produced in each. conversion zone is adjusted With relationto Ythe ratio of` hydrogen to carbon monoxide in the product streams from each conversion zone. To some extent the composition of the synthesis feed gas can be regulated for a gventotal quantityof hydrogen and carbon.rnonoxide. produced ineaoh conversion Zone` by ,adjustingv the-hydrogentocarbon .monoxide ratio Within. the` .aforementioned ranges of the separate streams fromthe. con-v Version zones;

Inorder to prevent. the build-.up ofnitrogen-in the system, particularly when using-air as a source of oxygen for combustion. unit -'i crm/'hen it is desirable to recycle CO2 alone or. in .a higher concentratonto reforming unitil, a portion of the recycle gases iscontinuously. tir-intermittently passed to a carcon dioxide l.absorption unit 36.3 through conduitsvfl and 3'? orv conduit 33.A In absorption unit 36 n.the gases .are contacted with a suitable solvent for the removal of carbon dioxide thereirom in vthe conventionall manner. Such solvents may comprisemonoethanolamine or other ethanolamines. Nitrogen and .other unabsorbed gases, such -as methane, removed from absorptionunit 36 -throughconduit 38. .and vented to the atmosphereor used-as fuel. Carbon dioxide is recoveredfrom the rich solvent by stripping, Aby reducing the total pressure-or by heating'and thentheresulting lean. solvent is returned for the absorption of more carbon dioxide. The desorbed carbon dioxide is removed from absorption unit 36 through conduit 39 and returned to recycle conduit 34 to be combined with recycle gases therein for return to either combustion unit l or reforming unit lll, or recycled directly to reforming unit ici through conduits 42 and 4l.

Certain valves, coolers, heaters, accumulators, distillation columns, pumps, etc. have been omitted from the drawings as a matter of convenience and their use and location will become obvious to those skilled in the art. The lengths of the conduits of the drawings are not proportional to the distance travelled but are merely diagrammatical. It is not intended to limit any particular location of inlets and outlets as shown in the drawings. The examples of composition of gases and theory in connection with this invention are offered as illustration and should not be construed to be unnecessarily limiting to the invention.

Various modifications and alterations of the process of the present invention may become app-arent to those skilled in the art without departing from the scope of this invention. For example, diiferent hydrocarbons may be converted in each reaction zone and the reaction eiiluent combined to produce a synthesis gas of the desired composition. Accordingly, in one modification propane is the major component of the feed stream to combustion unit 'l and methane is the major component of the feed to reforming unit I4. The effluents from each conversion zone have adifferent composition and these effluents are combined to produce a synthesis gas of the desired composition. A convenient and readily available source of propane for such a modification is from the synthesis reaction effluent itself.

I claim:

1. A process for the preparation of a hydrocarbon synthesis feed gas which comprises introducing a normally gaseous hydrocarbon from an external source into two separate conversion zones arranged in parallel, reacting the hydrocarbon with steam in the first conversion zone under reforming conditions to produce a gaseous eiiiuent comprising hydrogen and carbon monoxide in a relatively high mol ratio, simultaneously reacting the hydrocarbon with free oxygen in a second conversion zone under partial combustion conditions to producea gaseous effluent comprising hydrogen and carbon monoxide in a relatively low mol ratio, simultaneously introducing into one of said conversion zones a recycle product stream containing hydrogen and cornbined carbon of an efliuent from a synthesis reaction for the production of hydrocarbons from carbon monoxide and hydrogen, and combining the effluents from said conversion zones to produce a hydrocarbon synthesis feed gas.

2. A process for the preparation of a hydrocarbon synthesis feed gas which comprises introducing a normally gaseous hydrocarbon from an external source into two separate conversion zones arranged in parallel, reacting the hydrocarbon with steam in the first conversion zone under reforming conditions to produce a gaseous effluent comprising hydrogen and carbon monoxide in a mol ratio greater than about 2:1, simultaneously reacting the hydrocarbon with free oxygen in a second conversion zone under partial combustion conditions to produce a gaseous effluent comprising hydrogen and carbon monoxide in a mol yratio less than about 2:1, simultaneouslyintroducing into one of said conversion zones a recycle product stream containing hydrogen and combined carbon of an eluent from a synthesis reaction for the production of hydrocarbons from carbon monoxide and hydrogen and combining the eluents from said con- Version zones to produce a hydrocarbon synthesis feed gas.

3. A process for the preparation of a hydrocarbon synthesis of feed gas which comprises introducing a normally gaseous hydrocarbon from an external source into separate reforming and combustion zones arranged in parallel; reacting at relatively low pressure under reforming conditions steam, said gaseous hydrocarbon and a recycle product stream containing hydrogen and carbon dioxide of an effluent from an ironcatalyzed synthesis reaction for the production of hydrocarbons from carbon monoxide and hydrogen to produce in the reforming Zone a gaseous mixture comprising hydrogenv and carbon monoxide in a mol ratio greater than about 2:1; simultaneously reacting said gaseous hydrocarbon with free oxygen in the combustion chamber at relatively high pressure under partial` combustion conditions to produce a gaseous mixture comprising hydrogen and carbon monoxide in a mol ratio less than about 2:1, and combining the elliuents from the reforming and combustion zones to produce a hydrocarbon synthesis feed of the desired hydrogen-carbon monoxide mol ratio.

4. A process for the preparation of a hydrocarbon synthesis feed gas which comprises introducing a normally gaseous hydrocarbon from an external source into separate reforming and combustion zones arranged in parallel; reacting steam, said gaseous hydrocarbon and at least a portion of a recycle product stream containing hydrogen and carbon dioxide of an eiiluent from a synthesis reaction for the production of hydrocarbons from carbon monoxide and hydrogen to produce in the reforming zone a gaseous mixture comprising hydrogen and carbon monoxide in a mol ratio greater than about 2:1 at a temperature between about 1250 and about 2400 degrees Fahrenheit under a pressure between atmospheric and about 100 pounds per square inch gage; simultaneously reacting said gaseous hydrocarbon with free oxygen in the combustion zone under partial combustion conditions at a temperature between about 1700 and about 2600 degrees Fahrenheit under superatmospheric pressure to produce a gaseous mixture comprising hydrogen and carbon monoxide in a mol ratio less than about 2:1, and combining the euents from the reforming and combustion zones to produce a hydrocarbon synthesis feed gas of the desired hydrogen-carbon monoxide mol ratio.

5. A process according to claim 4 in which the normally gaseous hydrocarbon is methane.

6. A process for the preparation of a hydrocarbon synthesis feed gas which comprises introducing methane from an external source into separate and reforming combustion zones arranged in parallel; reacting steam, methane and a recycle product stream containing hydrogen and carbon dioxide of an eiuent from an ironcatalyzed synthesis reaction for the production of hydrocarbons from carbon monoxide and hydrogen to produce in the reforming zone a gaseous mixture comprising hydrogen and carbon monoxide in a mol ratio greater than about 2:1 at a temperatureV between about 1250 and about 2400 degrees Fahrenheit under a pressure between from the-A reforming and combustionzones toV produce a hydrocarbon synthesis feed gas of the Vdesired hydrogen-carbon monoxide mol ratio.

' 7processforthe production of a hydrocar- 'bonsynthesis feedvgas-which comprises reacting a hydrocarbon gas from 'an' external source con-.1f

taining propane as the majorcomponent-with free oxygen in a first conversion zone under partial combustion conditions to-produce a gaseous mixture comprising hydrogenand Vcarbon l monoxidein a relatively low mol ratio, simultaneously reactingv a hydrocarbon gas from an external source containing methane as the major component withl steam in-a separate second conversion' zone under reforming conditions toproduce a gaseous mixture comprising hydrogen and carbon rnonoxidednv a--relatively high mol ratio, simultaneously introducing into one or" said conversion zones-propane obtained from an eluent of -a synthesis reaction for the production of hydrocarbons from carbon monoxide and hydrogen,

and combining theeiiluents from said conversion Zones to producen hydrocarbon synthesis feed gas.

-8. A'process for the preparation ofv a hydrocarbon synthesis feed gas which comprises introducing a normally gaseous hydrocarbon from an external source into yseparate reforming and combustion zones arranged in paral-le1;-reacting steam, said gaseous hydrocarbon andf a recycle product stream containing hydrogen and carbon dioxide of an effluent from a synthesis reaction for the production of hydrocarbons from carbon monoxide and hydrogen from which water and organic compounds having a C3 and higher carbon content have been removed in the reforming zone at a temperature between about 1250 and about 2400 degrees Fahrenheit, under a pressure between atmospheric and about 100 pounds per square inch gage to produce a gaseous eluent comprising hydrogen and carbon monoxide in a mol ratio greater than about 2:1; simultaneously reacting in the combustion zone under partial combustion conditions at a temperature between about 1700 and about 2600 Adegrees Fahrenheit and a superatrnosphericpressure free oxygen with said gaseous hydrocarbon to produce a gaseous eflluent comprising hydrogen and carbon monoxide in a mol ratio less than about 2:1, and combining the effluents ci' the reforming and combustion zones to produce a synthesis feed gas of the desired hydrogencarbon monoxide mol ratio.

References Cited in the file 0f this patent UNITED STATES PATENTS Number Name Date 2,270,897 Roberts, Jr., et al. Jan. 27, 1942 2,274,064 Howard et al. Feb. 24, 1942 2,324,172 Parkhurst July 13, 1943 2,541,657 Lynch Feb. 13, 1951 

3. A PROCESS FOR THE PREPARATION OF A HYDROCARBON SYNTHESIS OF FEED GAS WHICH COMPRISES INTRODUCING A NORMALLY GASEOUS HYDROCARBON FROM AN EXTERNAL SOURCE INTO SEPARATE REFORMING AND COMBUSTION ZONES ARRANGED IN PARALLEL; REACTING AT RELATIVELY LOW PRESSURE UNDER REFORMING CONDITIONS STEAM, SAID GASEOUS HYDROCARBON AND A RECYCLE PRODUCT STREAM CONTAINING HYDROGEN AND CARBON DIOXIDE OF AN EFFLUENT FROM AN IRONCATALYZED SYNTHESIS REACTION FOR THE PRODUCTION OF HYDROCARBONS FROM CARBON MONOXIDE AND HYDROGEN TO PRODCUE IN THE REFORMING ZONE A GASEOUS MIXTURE COMPRSING HYDROGEN AND CARBON MONXIDE IN A MOL RATIO GRATER THAN ABOUT 2:1; SIMULTANEOUSLY REACTING SAID GASEOUS HYDROCARBON WITH FREE OXYGEN IN THE COMBUSTION CHAMBER AT RELATVIVELY HIGH PRESSURE UNDER PARTIAL COM- 